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Synthesis of Calix[4] arene Thia Derivative and Extraction Effect of Substituents on Mercury( Ⅱ) and Lead( Ⅱ)
摘    要:Calix4]arene derivatives have been reported to possess high selectivity for metal ions.In order to analyze the extraction effect of substituents on Hg~(2+)and Pb~(2+),calix4]arene derivatives containing hydroxyl,bromoethoxy and 1,11-dioxa-4,8-dithiahendecene were successfully synthesized,with their extraction effectiveness towards Hg~(2+)and Pb~(2+)were evaluated respectively.The results indicated that the phenolic hydroxyl in calix4]arene improved the extraction ability on Hg~(2+)by promoting the formation of the negative oxygen ions that could bind with Hg~(2+)by coordination and ionic bonds.The extraction ability of 5,17-dinitro-26,28-(1’,11’-dioxa-4’,8’-dithiahendecene)-calix4]arene(calix4]arene thia derivative)was improved slightly due to the better coordination capacity for metal ions after introduction of 1,11-dioxa-4,8-dithiahendecene,which was a chelate-binding centre.Regarding to Pb~(2+),only 1,11-dioxa-4,8-dithiahendecene on molecule contributed to extraction due to the coordination bond.Since the metal ion with higher charge-to-radius ratio could coordinate with one ligand more stably,Pb~(2+)with higher charge-to-radius ratio than Hg~(2+)was coordinated and extracted by the calix4]arene thia derivative more easily.Furthermore,extraction rates of the calix4]arene thia derivative on both ions(Hg~(2+)and Pb~(2+))increased with the increase of pH value in acidic aqueous system(pH7).

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